CN101312947B - Polyamide depolymerization method and polyamide monomer preparation method - Google Patents
Polyamide depolymerization method and polyamide monomer preparation method Download PDFInfo
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- CN101312947B CN101312947B CN2006800436936A CN200680043693A CN101312947B CN 101312947 B CN101312947 B CN 101312947B CN 2006800436936 A CN2006800436936 A CN 2006800436936A CN 200680043693 A CN200680043693 A CN 200680043693A CN 101312947 B CN101312947 B CN 101312947B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/12—Preparation of lactams by depolymerising polyamides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/20—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with hydrocarbons or halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
Disclosed is a commercially advantageous method for obtaining a monomer by performing a depolymerization reaction of a polyamide. Specifically disclosed is a method for obtaining a monomer through a depolymerization reaction of a polyamide, wherein the depolymerization reaction is performed in the presence of a hydrocarbon solvent. In addition, the depolymerization reaction is performed in the presence of water. The ratio of water relative to the total mass of the hydrocarbon solvent and water is not more than 30% by mass. The depolymerization reaction can be carried out without using a catalyst. Preferably, the depolymerization reaction is performed at a temperature not less than 300 DEG C and not more than 420 DEG C.
Description
Technical field
The present invention relates to can be by carrying out the next manufacture method that obtains the depolymerization method of monomeric polymeric amide and utilize the monomer of polyamide of this depolymerization method with high yield of depolymerization to polymeric amide.
Background technology
To carry out polymerization as the hexanolactam of raw material monomer, and can obtain nylon 6, be that the polyamide article of representative is utilized in each field in a large number with the form of nylon fiber, film, engineering plastics with nylon 6.Polyamide article after the utilization as waste by landfill or burning disposal.But, in recent years, from the aspect of environment protection and resources effective utilization, the whole bag of tricks that people utilize polyamide article in research again.
For example, put down in writing the method for in the presence of nitrogenous compound, in water, polymeric amide being carried out depolymerization in the patent documentation 1.But, use under the situation of a large amount of high temperature-high pressure waters, be created in sometimes relatively short during the problem of internal corrosion metal device.And, to consume lot of energy when behind depolymerization reaction, separating a large amount of water.And, need the high-grade drainage treatment equipment when discarding a large amount of water.
Patent documentation 1: Japanese kokai publication hei 8-301843 communique
Summary of the invention
The objective of the invention is to address the above problem, provide a kind of being used for to obtain the monomeric industrial method that helps simply and effectively by polymeric amide being carried out depolymerization.
The contriver furthers investigate the condition that Depolymerisation of polyamides is used, found that the monomeric rate of recovery in hydrocarbon solvent is higher than the situation in water far away, thereby has finished the present invention.That is, the present invention is the depolymerization method of polymeric amide, it is characterized in that, by Depolymerisation of polyamides is obtained in the monomer methods, carries out depolymerization reaction in the presence of hydrocarbon solvent.And the present invention is the manufacture method of monomer of polyamide, it is characterized in that, obtains described monomer of polyamide by in the presence of hydrocarbon solvent polymeric amide being carried out depolymerization reaction.
According to the present invention, can improve the monomeric rate of recovery significantly.And, can prevent the corrosion of locking apparatus by the organic solvent that uses hydro carbons.And then, because the vaporization heat of hydrocarbon solvent is little, thereby can reduce the cost of energy that is used to reclaim hydrocarbon solvent.And hydrocarbon solvent can use repeatedly, and also can be used as fuel effectively utilize when discarded.Can on industrial level, realize thus in the past by the Reuse of materials of the polyamide article of landfill or burning disposal.
Embodiment
Explain the present invention below.
Employed polymeric amide is the polymkeric substance that is combined with two above acid amides (C (O) NH-) key among the present invention.More particularly, be that diamines and dicarboxylic acid become the catenate polymer body or the chain polymer body that obtains by the monomer ring-opening polymerization to amino in a molecule as the hexanolactam and the shape behind the carboxyl dehydration condensation and cyclization by amido linkage.And, the polymerization degree of polymeric amide is not particularly limited, also can be oligopolymer as low-grade polymer.As oligopolymer, can enumerate catemer (dimer of hexosamine to about heptamer) and ring bodies (about dimer to nine aggressiveness).And polymeric amide can be a kind of, also can two or more mixing exist.For example can enumerate nylon 6, nylon 66, Ni Long11 and nylon 12 etc., preferably use nylon 6.As its concrete example, can enumerate: the product beyond the waste of nylon 6 fiber carpet, the specification that produces when switching the grade of product when nylon 6 is made in the hexanolactam successive polymerization, from the distillation residue that remove the residue that contains oligopolymer after anhydrating the rinse water behind the hot water cleaning cleaning polyalcohol, produce during the continuous still battery hexanolactam in as the operation of monomeric hexanolactam in manufacturing etc.
Below hydrocarbon solvent is described.As the hydrocarbon solvent that uses among the present invention, no matter be that aliphatics or aromatic series can use.As concrete example, can enumerate aliphatic hydrocarbons such as normal hexane, normal heptane, hexanaphthene; Aromatic hydrocarbons such as benzene, toluene etc.Wherein preferably use toluene.
When in the presence of hydrocarbon solvent, polymeric amide being carried out depolymerization reaction, can carry out depolymerization reaction having hydrocarbon solvent and exist simultaneously under the condition of water.Can shorten the required reaction times of depolymerization thus.At this moment, water greater than 0 smaller or equal to 30 quality %, is preferably 1 quality %～20 quality % for the ratio of the total mass of hydrocarbon solvent and water.If water surpasses 30 quality % for the ratio of the total mass of hydrocarbon solvent and water, then easily during relatively shorter in the corrosion of generation metal device, so not preferred.
Polymeric amide greater than 0 smaller or equal to 50 quality %, is preferably 10 quality %～40 quality % with respect to the ratio of the total mass of polymeric amide and hydrocarbon solvent and water.
In the depolymerization reaction of polymeric amide of the present invention, can use catalyzer such as acid, alkali.But can under the situation of not using catalyzer, realize high recovery yield of monomer.Thereby the supply arrangement that does not need catalyzer, and the depolymerization reaction system becomes simply, and then do not need removing-recovery process of catalyzer, thereby become the technology of industrial excellence.
The temperature of carrying out depolymerization reaction is 300 ℃～420 ℃, is preferably 300 ℃～400 ℃, is preferably 350 ℃～370 ℃ especially.The temperature that is lower than 300 ℃ is not preferred owing to the depolymerization reaction that can not fully carry out polymeric amide.On the other hand, when surpassing 420 ℃, the monomer after the depolymerization is understood further thermolysis and is reduced the monomeric rate of recovery, thereby not preferred.
The time of depolymerization reaction is 5 minutes～4 hours, is preferably 1 hour～2 hours.Can reclaim monomer with the rate of recovery that is higher than in the past thus.
For the treatment solution behind the depolymerization reaction, in the hydrocarbon solvent recovery process, reclaim hydrocarbon solvent.As the means that reclaim hydrocarbon solvent, (decompression) water distilling apparatus such as the hurried tripping device that can enumerate the simple distillation device, constitute by flash tank etc., distillation tower etc.Carrying out under sealed state under the situation of depolymerization reaction, is the state of High Temperature High Pressure in the reaction vessel.Thereby, utilize pressure regulator valve to make the interior step-down of reaction vessel after the reaction with the temperature more than the boiling point that reaches hydrocarbon solvent, can flash distillation hydrocarbon solvent and recovery by this simple method.Can reduce energy cost thus.Hydrocarbon solvent after the flash distillation utilizes condenser condenses.Hydrocarbon solvent through condensation is reused in depolymerization reaction.
Residue for behind the recovery hydrocarbon solvent reclaims monomer in the MONOMER RECOVERY operation.As the MONOMER RECOVERY means, can enumerate simple distillation device, distillation tower etc. (decompression) water distilling apparatus, thin film evaporation unit etc.Wherein, preferably use thin film evaporation unit owing to can prevent monomeric thermal degradation when.For example, in the situation that the hexanolactam that obtains by depolymerization nylon 6 is handled with thin film evaporation unit, recovered temperature is 80 ℃～120 ℃, and the pressure of cat head is 0.05kPaA～2.66kPaA (A represents absolute pressure).Monomer through reclaiming can directly be used for the manufacturing of polymeric amide once more, or is used for the manufacturing of polymeric amide after utilizing rectifying, recrystallize, distillation means further to make with extra care once more.
On the other hand, in the MONOMER RECOVERY operation, reclaim not contain behind the monomer and can be supplied to the depolymerization reaction container once more by the residue of the unreacted reactant of depolymerization.Can further improve the monomeric rate of recovery thus.
Embodiment
Enumerate embodiment below, illustrate in greater detail the present invention, but the present invention is not subjected to any restriction of following embodiment, can in the scope that does not break away from aim of the present invention, change and implement.
(embodiment 1)
As reactor, use the reaction tubes of volume as SUS316 (stainless steel) system of 10mL.In reaction tubes, add 0.3g nylon 6 (emerging nylon6 chips 1022B that produce of space portion) and 4g toluene (synthesize with (dehydration) with the pure medicine of the light machine that is shaped on, water-content is 10ppm).Then, with sealing behind the air in the headspace in the argon replaces reaction tubes.Reaction tubes after the sealing is statically placed in the electric furnace that is heated to 370 ℃, heated 6 hours.The interior pressure of reaction tubes this moment is 7.6MPaG (G represents gauge pressure).After the heating reaction tubes is taken out from electric furnace, reaction tubes be impregnated in the water, be cooled to free air temperature thus.From cooled reaction tubes, take out content, the ε-Ji Neixianan that is contained is carried out quantitatively.
Utilize gas chromatograph (the system GC-14B of Shimadzu Seisakusho Ltd.) that ε-Ji Neixianan is carried out quantitatively.Calculate the rate of recovery of ε-Ji Neixianan according to following formula.The results are shown in table 1.The rate of recovery of hexanolactam is 74.1 weight %.This expression is compared the rate of recovery with the situation of water in comparative example 1 as follows and the comparative example 2 and is further enhanced.And,, find to have kept stainless gloss to carrying out Visual Confirmation in the reacted reaction vessel.
[rate of recovery of ε-Ji Neixianan (quality %)]
=[(ε-Ji Neixianan in the reaction mixture (quality %)) * (nylon 6 before the reaction and the total mass (g) of solvent and catalyzer)]/(quality (g) of the nylon 6 before the reaction) * 100
Need to prove, not use under the situation of catalyzer that the quality of catalyzer is 0 (g).
(comparative example 1 and comparative example 2)
Make water replace toluene, will change 1 hour heat-up time into (comparative example 1) and 2 hours (comparative example 2), in addition, use the method identical to carry out depolymerization reaction, obtain the rate of recovery of hexanolactam with embodiment 1.Pressure in the reaction tubes is 24.8MPaG.The results are shown in table 1.Its result, the rate of recovery of hexanolactam is lower than embodiment 1.And,, find that stainless gloss partly disappears, slightly black to carrying out Visual Confirmation in the reacted reaction vessel.
(embodiment 2～31)
As shown in table 1, except changing various conditions, use the method identical to carry out depolymerization reaction with embodiment 1.For the pressure in the reaction tubes, embodiment 6～8 is 10MPaG, and embodiment 13 and 14 is 8.4MPaG, embodiment 15 and 16 is 11.3MPaG, and embodiment 17 and 18 is 12.9MPaG, and embodiment 19 and 20 is 14.8MPaG, embodiment 21 and 22 is 17.9MPaG, and embodiment 28 is 20.7MPaG.The results are shown in table 1.The result shows that the rate of recovery of hexanolactam is all very high.And,, find to have kept stainless gloss to carrying out Visual Confirmation in the reacted reaction vessel.
(embodiment 32～35)
Use oligopolymer to replace nylon 6 to carry out depolymerization reaction.So-called herein oligopolymer is meant, carries out hot water behind the polymerization ε-Ji Neixianan and cleans, and by the residue that removes in the rinse water after anhydrating, wherein contains the oligopolymer of unreacted ε-Ji Neixianan and ε-Ji Neixianan.Consisting of of concrete oligopolymer: ε-Ji Neixianan is that 22.5 quality %, hexosamine are that 3.1 quality %, cyclic dimer are that 16.6 quality %, cyclic trimer are that 21.1 quality %, cyclic tetramer are that 13.4 quality %, ring-type pentamer are that 7.3 quality %, ring-type six aggressiveness are that 1.8 quality %, ring-type heptamer are 1.4 quality %, other composition of containing the chain oligopolymer is 12.8 quality %.Except change condition as shown in table 1, use the method identical to carry out depolymerization reaction with embodiment 1.For the pressure in the reaction tubes, embodiment 32～34 is 14.8MPaG, and embodiment 35 is 20.7MPaG.The results are shown in table 1.The result shows that the rate of recovery of hexanolactam is very high.And,, find to have kept stainless gloss to carrying out Visual Confirmation in the reacted reaction vessel.
(embodiment 36)
Use normal hexane (Wako Pure Chemical Industries, Ltd. makes, and water-content is 10ppm) to replace toluene, and then change condition as shown in table 1, in addition, use the method identical to carry out depolymerization reaction with embodiment 1.Pressure in the reaction tubes is 14.9MPaG.The results are shown in table 1.The result shows that the rate of recovery of hexanolactam is very high.And,, find to have kept stainless gloss to carrying out Visual Confirmation in the reacted reaction vessel.
[table 1]
| The kind of polymeric amide | Polymeric amide (g) | The kind of hydrocarbon solvent | Hydrocarbon solvent (g) | Water (g) | Temperature (℃) | Heat-up time (hour) | The rate of recovery of hexanolactam (with respect to the quality % of nylon) | |
| Embodiment 1 | Nylon 6 | 0.3 | Toluene | 4.0 | 0.0 | 370 | 6 | ?74.1 |
| Embodiment 2 | Nylon 6 | 0.3 | Toluene | 3.99 | 0.01 | 370 | 2 | ?72.3 |
| Embodiment 3 | Nylon 6 | 0.3 | Toluene | 3.95 | 0.05 | 370 | 1 | ?83.6 |
| Embodiment 4 | Nylon 6 | 0.3 | Toluene | 3.95 | 0.05 | 370 | 2 | ?91.0 |
| Embodiment 5 | Nylon 6 | 0.3 | Toluene | 3.95 | 0.05 | 370 | 3 | ?93.5 |
| Embodiment 6 | Nylon 6 | 0.3 | Toluene | 3.9 | 0.1 | 370 | 1 | ?89.9 |
| Embodiment 7 | Nylon 6 | 0.3 | Toluene | 3.9 | 0.1 | 370 | 2 | ?94.5 |
| Embodiment 8 | Nylon 6 | 0.3 | Toluene | 3.9 | 0.1 | 370 | 3 | ?92.9 |
| Embodiment 9 | Nylon 6 | 0.6 | Toluene | 3.9 | 0.1 | 370 | 2 | ?93.7 |
| Embodiment 10 | Nylon 6 | 1.2 | Toluene | 3.9 | 0.1 | 370 | 2 | ?82.0 |
| Embodiment 11 | Nylon 6 | 0.3 | Toluene | 3.8 | 0.2 | 370 | 1 | ?91.0 |
| Embodiment 12 | Nylon 6 | 0.3 | Toluene | 3.8 | 0.2 | 370 | 2 | ?92.0 |
| Embodiment 13 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 300 | 1 | ?82.0 |
| Embodiment 14 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 300 | 2 | ?91.5 |
| Embodiment 15 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 330 | 1 | ?94.5 |
| Embodiment 16 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 330 | 2 | ?93.1 |
| Embodiment 17 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 350 | 1 | ?96.6 |
| Embodiment 18 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 350 | 2 | ?94.3 |
| Embodiment 19 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 370 | 1 | ?96.9 |
| Embodiment 20 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 370 | 2 | ?93.1 |
| Embodiment 21 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 400 | 1 | ?93.3 |
| Embodiment 22 | Nylon 6 | 0.3 | Toluene | 3.6 | 0.4 | 400 | 2 | ?94.6 |
| Embodiment 23 | Nylon 6 | 1.2 | Toluene | 3.6 | 0.4 | 330 | 2 | ?87.1 |
| Embodiment 24 | Nylon 6 | 1.2 | Toluene | 3.6 | 0.4 | 350 | 2 | ?89.0 |
| Embodiment 25 | Nylon 6 | 1.2 | Toluene | 3.6 | 0.4 | 370 | 1 | ?88.5 |
| Embodiment 26 | Nylon 6 | 1.2 | Toluene | 3.6 | 0.4 | 370 | 2 | ?94.3 |
| Embodiment 27 | Nylon 6 | 2.0 | Toluene | 2.7 | 0.3 | 370 | 2 | ?61.3 |
| Embodiment 28 | Nylon 6 | 0.3 | Toluene | 3.2 | 0.8 | 370 | 1 | ?94.4 |
| Embodiment 29 | Nylon 6 | 1.2 | Toluene | 3.2 | 0.8 | 370 | 1 | ?89.0 |
| Embodiment 30 | Nylon 6 | 1.2 | Toluene | 3.2 | 0.8 | 370 | 2 | ?87.3 |
| Embodiment 31 | Nylon 6 | 1.2 | Toluene | 3.2 | 0.8 | 370 | 1 | ?87.0 |
| Embodiment 32 | Oligopolymer | 1.26 | Toluene | 3.6 | 0.4 | 370 | 1 | ?85.5 |
| Embodiment 33 | Oligopolymer | 1.26 | Toluene | 3.6 | 0.4 | 370 | 2 | ?88.5 |
| Embodiment 34 | Oligopolymer | 1.26 | Toluene | 3.6 | 0.4 | 370 | 3 | ?91.0 |
| Embodiment 35 | Oligopolymer | 1.26 | Toluene | 3.2 | 0.8 | 370 | 2 | ?81.7 |
| Embodiment 36 | Nylon 6 | 1.2 | Normal hexane | 3.6 | 0.4 | 370 | 1 | ?84.2 |
| Comparative example 1 | Nylon 6 | 0.3 | - | 0 | 4.0 | 370 | 1 | ?67.7 |
| Comparative example 2 | Nylon 6 | 0.3 | - | 0 | 4.0 | 370 | 2 | ?56.1 |
(embodiment 37～69)
Below, the kind of change hydrocarbon solvent as shown in table 2 is carried out the depolymerization of nylon 6.Use the hydrocarbon solvent beyond the toluene, and make also comprise 3 hours heat-up time except that 1 hour and 2 hours, in addition, utilization and water are that embodiment 19 and the 20 identical methods of 10 quality % are carried out depolymerization reaction for the ratio of the total mass of hydrocarbon solvent and water.Hydrocarbon solvent as beyond the toluene has used normal hexane, hexanaphthene, n-dodecane, normal heptane, octane, cyclooctane, n-tridecane, n-tetradecane, Pentadecane, whiteruss (with the pure medicine system superfine of light), naphthane (with the pure medicine system one-level of light).In addition, the pressure in the reaction tubes of embodiment 64 is 5.1MPaG.As shown in table 2, the result shows that even under the situation of using toluene hydrocarbon solvent in addition, the rate of recovery of hexanolactam is also very high.And,, find to have kept stainless gloss to carrying out Visual Confirmation in the reacted reaction vessel.
[table 2]
| The kind of polymeric amide | Polymeric amide (g) | Solvent types | Hydrocarbon solvent (g) | Water (g) | Temperature (℃) | Heat-up time (hour) | The rate of recovery of hexanolactam (with respect to the quality % of nylon) | |
| Embodiment 19 | Nylon 6 | 0.3 | 10% water/toluene | 3.6 | 0.4 | 370 | 1 | ?96.93 |
| Embodiment 20 | Nylon 6 | 0.3 | 10% water/toluene | 3.6 | 0.4 | 370 | 2 | ?93.14 |
| Embodiment 37 | Nylon 6 | 0.3 | 10% water/normal hexane | 3.6 | 0.4 | 370 | 1 | ?91.10 |
| Embodiment 38 | Nylon 6 | 0.3 | 10% water/normal hexane | 3.6 | 0.4 | 370 | 2 | ?91.16 |
| Embodiment 39 | Nylon 6 | 0.3 | 10% water/normal hexane | 3.6 | 0.4 | 370 | 3 | ?92.61 |
| Embodiment 40 | Nylon 6 | 0.3 | 10% water/hexanaphthene | 3.6 | 0.4 | 370 | 1 | ?90.46 |
| Embodiment 41 | Nylon 6 | 0.3 | 10% water/hexanaphthene | 3.6 | 0.4 | 370 | 2 | ?91.19 |
| Embodiment 42 | Nylon 6 | 0.3 | 10% water/hexanaphthene | 3.6 | 0.4 | 370 | 3 | ?90.24 |
| Embodiment 43 | Nylon 6 | 0.3 | 10% water/n-dodecane | 3.6 | 0.4 | 370 | 1 | ?95.73 |
| Embodiment 44 | Nylon 6 | 0.3 | 10% water/n-dodecane | 3.6 | 0.4 | 370 | 2 | ?95.23 |
| Embodiment 45 | Nylon 6 | 0.3 | 10% water/n-dodecane | 3.6 | 0.4 | 370 | 3 | ?94.95 |
| Embodiment 46 | Nylon 6 | 0.3 | 10% water/normal heptane | 3.6 | 0.4 | 370 | 1 | ?91.88 |
| Embodiment 47 | Nylon 6 | 0.3 | 10% water/normal heptane | 3.6 | 0.4 | 370 | 2 | ?92.01 |
| Embodiment 48 | Nylon 6 | 0.3 | 10% water/normal heptane | 3.6 | 0.4 | 370 | 3 | ?92.05 |
| Embodiment 49 | Nylon 6 | 0.3 | 10% water/octane | 3.6 | 0.4 | 370 | 1 | ?89.70 |
| Embodiment 50 | Nylon 6 | 0.3 | 10% water/octane | 3.6 | 0.4 | 370 | 2 | ?91.32 |
| Embodiment 51 | Nylon 6 | 0.3 | 10% water/octane | 3.6 | 0.4 | 370 | 3 | ?93.98 |
| Embodiment 52 | Nylon 6 | 0.3 | 10% water/cyclooctane | 3.6 | 0.4 | 370 | 1 | ?92.54 |
| Embodiment 53 | Nylon 6 | 0.3 | 10% water/cyclooctane | 3.6 | 0.4 | 370 | 2 | ?92.13 |
| Embodiment 54 | Nylon 6 | 0.3 | 10% water/cyclooctane | 3.6 | 0.4 | 370 | 3 | ?91.93 |
| Embodiment 55 | Nylon 6 | 0.3 | 10% water/n-tridecane | 3.6 | 0.4 | 370 | 1 | ?93.67 |
| Embodiment 56 | Nylon 6 | 0.3 | 10% water/n-tridecane | 3.6 | 0.4 | 370 | 2 | ?92.17 |
| Embodiment 57 | Nylon 6 | 0.3 | 10% water/n-tridecane | 3.6 | 0.4 | 370 | 3 | ?92.67 |
| Embodiment 58 | Nylon 6 | 0.3 | 10% water/n-tetradecane | 3.6 | 0.4 | 370 | 1 | ?92.96 |
| Embodiment 59 | Nylon 6 | 0.3 | 10% water/n-tetradecane | 3.6 | 0.4 | 370 | 2 | ?93.19 |
| Embodiment 60 | Nylon 6 | 0.3 | 10% water/n-tetradecane | 3.6 | 0.4 | 370 | 3 | ?93.27 |
| Embodiment 61 | Nylon 6 | 0.3 | 10% water/Pentadecane | 3.6 | 0.4 | 370 | 1 | ?93.16 |
| Embodiment 62 | Nylon 6 | 0.3 | 10% water/Pentadecane | 3.6 | 0.4 | 370 | 2 | ?94.11 |
| Embodiment 63 | Nylon 6 | 0.3 | 10% water/Pentadecane | 3.6 | 0.4 | 370 | 3 | ?93.78 |
| Embodiment 64 | Nylon 6 | 0.3 | 10% water/whiteruss | 3.6 | 0.4 | 370 | 1 | ?73.50 |
| Embodiment 65 | Nylon 6 | 0.3 | 10% water/whiteruss | 3.6 | 0.4 | 370 | 2 | ?81.24 |
| Embodiment 66 | Nylon 6 | 0.3 | 10% water/whiteruss | 3.6 | 0.4 | 370 | 3 | ?87.21 |
| Embodiment 67 | Nylon 6 | 0.3 | 10% water/naphthane | 3.6 | 0.4 | 370 | 1 | ?90.50 |
| Embodiment 68 | Nylon 6 | 0.3 | 10% water/naphthane | 3.6 | 0.4 | 370 | 2 | ?91.50 |
| Embodiment 69 | Nylon 6 | 0.3 | 10% water/naphthane | 3.6 | 0.4 | 370 | 3 | ?91.62 |
(embodiment 70～74)
Below, change water as shown in table 3 carries out the depolymerization of nylon 6 for the ratio of the total mass of hydrocarbon solvent and water.Except changing the ratio of water, utilize and heat the identical method of 1 hour embodiment 3,6,11,19 and 28 at 370 ℃ and carry out depolymerization reaction for the total mass of hydrocarbon solvent and water.As shown in table 3, the result shows, water for the ratio of the total mass of hydrocarbon solvent and water greater than 0 rate of recovery that can obtain very high hexanolactam during smaller or equal to 30 quality %.And then show that when water was 1 quality %～20 quality % for the ratio of the total mass of hydrocarbon solvent and water, the rate of recovery of hexanolactam was high especially.And, be embodiment 3,6,11,19,28 and 70 below the 30 quality % for water for the ratio of the total mass of hydrocarbon solvent and water, to carrying out Visual Confirmation in the reacted reaction vessel, find to have kept stainless gloss.
[table 3]
| The kind of polymeric amide | Polymeric amide (g) | Solvent types | Hydrocarbon solvent (g) | Water (g) | Temperature (℃) | Heat-up time (hour) | The rate of recovery of hexanolactam (with respect to the quality % of nylon) | |
| Embodiment 3 | Nylon 6 | 0.3 | 1.25% water/toluene | 3.95 | 0.05 | 370 | 1 | ?83.64 |
| Embodiment 6 | Nylon 6 | 0.3 | 2.5% water/toluene | 3.9 | 0.1 | 370 | 1 | ?89.90 |
| Embodiment 11 | Nylon 6 | 0.3 | 5% water/toluene | 3.8 | 0.2 | 370 | 1 | ?90.98 |
| Embodiment 19 | Nylon 6 | 0.3 | 10% water/toluene | 3.6 | 0.4 | 370 | 1 | ?96.93 |
| Embodiment 28 | Nylon 6 | 0.3 | 20% water/toluene | 3.2 | 0.8 | 370 | 1 | ?94.42 |
| Embodiment 70 | Nylon 6 | 0.3 | 30% water/toluene | 2.8 | 1.2 | 370 | 1 | ?86.46 |
| Embodiment 71 | Nylon 6 | 0.3 | 40% water/toluene | 2.4 | 1.6 | 370 | 1 | ?86.13 |
| Embodiment 72 | Nylon 6 | 0.3 | 50% water/toluene | 2.0 | 2.0 | 370 | 1 | ?84.67 |
| Embodiment 73 | Nylon 6 | 0.3 | 60% water/toluene | 1.6 | 2.4 | 370 | 1 | ?81.81 |
| Embodiment 74 | Nylon 6 | 0.3 | 70% water/toluene | 1.2 | 2.8 | 370 | 1 | ?73.24 |
(embodiment 75～77)
Below, the temperature of depolymerization reaction is carried out in change as shown in table 4, carries out the depolymerization of nylon 6.Except the temperature of depolymerization reaction was carried out in change, utilizing with water was that the identical method of the embodiment 13,15,17,19 and 21 of 10 quality % is carried out depolymerization reaction for the ratio of the total mass of hydrocarbon solvent and water.As shown in table 4, the result shows, even change the rate of recovery that the temperature of carrying out depolymerization reaction also can obtain very high hexanolactam.And then show that can obtain the rate of recovery of extra high hexanolactam when the temperature of carrying out depolymerization reaction is 300 ℃～420 ℃, the rate of recovery of hexanolactam was high when the temperature of carrying out depolymerization reaction was 350 ℃～370 ℃.And,, find to have kept stainless gloss to carrying out Visual Confirmation in the reacted reaction vessel.
[table 4]
| The kind of polymeric amide | Polymeric amide (g) | Solvent types | Hydrocarbon solvent (g) | Water (g) | Temperature (℃) | Heat-up time (hour) | The rate of recovery of hexanolactam (with respect to the quality % of nylon) | |
| Embodiment 75 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 280 | 1 | ?72.18 |
| Embodiment 13 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 300 | 1 | ?82.04 |
| Embodiment 15 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 330 | 1 | ?94.54 |
| Embodiment 17 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 350 | 1 | ?96.60 |
| Embodiment 19 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 370 | 1 | ?96.93 |
| Embodiment 21 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 400 | 1 | ?93.27 |
| Embodiment 76 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 420 | 1 | ?89.66 |
| Embodiment 77 | Nylon 6 | ?0.3 | 10% water/toluene | 3.6 | 0.4 | 450 | 1 | ?71.69 |
Industrial applicibility
The present invention can obtain utilizing when coming with high-recovery recovery monomer by the depolymerization polyamide article.
Claims (3)
1. the depolymerization method of a nylon 6, it is characterized in that, described depolymerization method is included in sealed state, do not use catalyzer, in the presence of hydrocarbon solvent and water, by nylon 6 is carried out the operation that depolymerization obtains caprolactam, wherein, water is 1 quality %～20 quality % for the ratio of the total mass of hydrocarbon solvent and water, carries out depolymerization reaction at 350 ℃～420 ℃.
2. the depolymerization method of nylon 6 as claimed in claim 1, wherein, described hydrocarbon solvent is a toluene.
3. the manufacture method of a caprolactam is characterized in that, the depolymerization method by claim 1 or 2 described nylon 6 obtains caprolactam.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP339752/2005 | 2005-11-25 | ||
| JP2005339752 | 2005-11-25 | ||
| PCT/JP2006/322157 WO2007060828A1 (en) | 2005-11-25 | 2006-11-07 | Method for depolymerizing polyamide and method for producing monomer of polyamide |
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| CN101312947A CN101312947A (en) | 2008-11-26 |
| CN101312947B true CN101312947B (en) | 2011-04-13 |
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| EP (1) | EP1975156B1 (en) |
| JP (1) | JP4957555B2 (en) |
| CN (1) | CN101312947B (en) |
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| WO (1) | WO2007060828A1 (en) |
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| CN104538549A (en) * | 2014-12-30 | 2015-04-22 | 厦门大学 | Manufacturing method of SrTiO3 single-crystal resistance switch device |
| US10843429B2 (en) | 2018-05-21 | 2020-11-24 | O2 Partners, Llc | Biodegradable, industrially compostable, and recyclable injection molded microcellular flexible foams |
| EP3797022A4 (en) | 2018-05-21 | 2022-02-23 | O2 Partners, LLC | Biodegradable and industrially compostable injection moulded microcellular flexible foams, and a method of manufacturing the same |
| ES2955329T3 (en) * | 2019-05-21 | 2023-11-30 | O2 Partners Llc | Biodegradable, industrially compostable and recyclable injection molded flexible microcell foams |
| NL2027900B1 (en) | 2021-04-01 | 2022-10-17 | Ioniqa Tech B V | Method for the depolymerization of polycaprolactam processing waste to form caprolactam |
| WO2023120427A1 (en) * | 2021-12-23 | 2023-06-29 | 旭化成株式会社 | Depolymerization method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892624A (en) * | 1987-09-05 | 1990-01-09 | Basf Aktiengesellschaft | Workup of distillation residues from the purification of caprolactam |
| CN1167483A (en) * | 1994-12-01 | 1997-12-10 | 巴斯福股份公司 | Process for preparing caprolactam |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000034363A (en) * | 1998-07-21 | 2000-02-02 | Toray Ind Inc | Recycling of nylon 6 products |
| JP2000191638A (en) * | 1998-12-28 | 2000-07-11 | Ube Ind Ltd | Method for recording epsilon-caprolactam and recovery facility therefor |
| JP2001316479A (en) * | 2000-05-10 | 2001-11-13 | Diabond Industry Co Ltd | Method for producing polyester-added polyvinyl alcohol/ vinyl acetate copolymer |
| DE10041198B4 (en) * | 2000-08-23 | 2004-01-15 | Symrise Gmbh & Co. Kg | Process for the preparation of macrocyclic esters |
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2006
- 2006-11-07 EP EP20060823070 patent/EP1975156B1/en not_active Expired - Fee Related
- 2006-11-07 JP JP2007546394A patent/JP4957555B2/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892624A (en) * | 1987-09-05 | 1990-01-09 | Basf Aktiengesellschaft | Workup of distillation residues from the purification of caprolactam |
| CN1167483A (en) * | 1994-12-01 | 1997-12-10 | 巴斯福股份公司 | Process for preparing caprolactam |
Non-Patent Citations (2)
| Title |
|---|
| JP昭46-31541 1971.09.13 |
| JP特开2000-191638A 2000.07.11 |
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| DE602006020497D1 (en) | 2011-04-14 |
| WO2007060828A1 (en) | 2007-05-31 |
| EP1975156B1 (en) | 2011-03-02 |
| CN101312947A (en) | 2008-11-26 |
| EP1975156A4 (en) | 2009-04-22 |
| EP1975156A1 (en) | 2008-10-01 |
| JPWO2007060828A1 (en) | 2009-05-07 |
| JP4957555B2 (en) | 2012-06-20 |
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